Solar cells are generally made of semiconductor materials, such as silicon (Si), which convert sunlight into useful electrical energy. A solar cell is in generally made of thin wafers of Si in which the required PN junction is formed by diffusing phosphorus (P) from a suitable phosphorus source into a p-type Si wafer. The side of the silicon wafer on which sunlight is incident is generally coated with an anti-reflective coating (ARC) to prevent reflective loss of sunlight. This ARC increases the solar cell efficiency. A two dimensional electrode grid pattern known as a front contact makes a connection to the n-side of silicon, and a coating of predominantly aluminum (Al) makes connection to the p-side of the silicon (back contact). Further, contacts known as silver rear contacts, made out of silver or silver-aluminum paste are printed and fired on the p-side of silicon to enable soldering of tabs that electrically connect one cell to the next in a solar cell module. These contacts are the electrical outlets from the PN junction to the outside load.
Conventional pastes for solar cell contacts contain lead frits. Inclusion of PbO in a glass component of a solar cell paste has the desirable effects of (a) lowering the firing temperature of paste compositions, (b) facilitating interaction with the silicon substrate and, upon firing, helping to form low resistance contacts with silicon. For these and other reasons PbO is a significant component in many conventional solar cell paste compositions. However, in light of environmental concerns, the use of PbO (as well as CdO), in paste compositions is now largely avoided whenever possible. Hence a need exists in the photovoltaic industry for lead-free and cadmium-free paste compositions, which afford desirable properties using lead-free and cadmium-free glasses in solar cell contact pastes.
Presently, a typical solar cell silicon wafer is about 200-300 microns thick, and the trend is toward thinner wafers. Because the wafer cost is about 60% of the cell fabrication cost, the industry is seeking ever-thinner wafers, approaching 150 microns. As the wafer thickness decreases, the tendency toward bowing (bending) of the cell due to the sintering stress increases, as well as bowing induced by the great difference in the thermal coefficients of expansion (TCE) between aluminum (232×10−7/° C. @ 20-300° C.) and silicon (26×10−7/° C. @ 20-300° C.).
Known methods of mitigating silicon wafer bowing include reduction of aluminum content during screen-printing that causes incomplete formation of Back Surface Field (BSF) layers and requires a higher firing temperature to achieve the same results. Chemical (acid) etching has been used to remove the Al—Si alloy that forms after firing the aluminum paste. This is just another step in the manufacturing process that leads to additional cost.
Another approach is to use additives to reduce the thermal expansion mismatch between the Al layer and the silicon wafer. However, a drawback is a reduction in back surface passivation quality and a concomitant reduction in solar cell performance. Partial covers, where only a portion of the back side of the wafer is coated with aluminum, have been used on the back surface to counteract bowing, which causes a reduction in cell performance.
Finally, another conventional way to reduce or eliminate bowing is cooling a finished solar cell from room temperature to ca. −50° C. for several seconds after firing. With the accompanying plastic deformation of the Al—Si paste matrix, bowing is largely eliminated, but this represents an additional process step, and there is a high danger of breakage from thermal stressing.
Hence a need exists in the photovoltaic industry for a low-bow, lead-free, high-performance Al paste that can create a sufficient aluminum back surface field in a solar cell contact, a method of making such a contact, and the Al paste from which such a BSF is formed.